EP1293485B1 - Method for treating industrial waste water - Google Patents

Method for treating industrial waste water Download PDF

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Publication number
EP1293485B1
EP1293485B1 EP20020100091 EP02100091A EP1293485B1 EP 1293485 B1 EP1293485 B1 EP 1293485B1 EP 20020100091 EP20020100091 EP 20020100091 EP 02100091 A EP02100091 A EP 02100091A EP 1293485 B1 EP1293485 B1 EP 1293485B1
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EP
European Patent Office
Prior art keywords
wastewater
nanofiltration
biological
passing
waste water
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EP20020100091
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German (de)
French (fr)
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EP1293485A1 (en
Inventor
Manfred Rick
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Ford Global Technologies LLC
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Ford Global Technologies LLC
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Priority to DE50206295T priority Critical patent/DE50206295D1/en
Priority to ES02100091T priority patent/ES2261595T3/en
Priority to EP20020100091 priority patent/EP1293485B1/en
Priority to US10/248,589 priority patent/US6787037B2/en
Publication of EP1293485A1 publication Critical patent/EP1293485A1/en
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/04—Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/04—Aerobic processes using trickle filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/06—Aerobic processes using submerged filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness
    • C02F5/06—Softening water by precipitation of the hardness using calcium compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention relates to a method for the treatment of waste water from the metalworking industry, preferably suitable for treating the wastewater so that it can be supplied to the production again.
  • the abovementioned wastewater is essentially contaminated with the following pollutants (the framework wastewater VwV, Appendix 40) serves as the basis: Table 1: Pollutants in industrial wastewater and their treatment options parameter Treatment method in the ABA heavy metals Flocculation / Precipitation as Metallhydroxidschlamm, bisulfide precipitation, ion exchanger. CKW, LHKW activated carbon complexing avoidance hydrocarbons membrane processes CSB Biological degradation stage
  • the wastewater After passing through a suitable ABA, the wastewater is first passed through a sand filter. Thereafter, the waste water passes through a fixed bed reactor for the removal of the COD. Subsequently, the Ca ions are exchanged for Na ions in two alternating softening columns. The final nanofiltration then serves to set all the quality parameters of the wastewater that is then purified.
  • the disadvantage here is to assess that in this method, a relatively large amount of wastewater is obtained as well as an additional wastewater stream is created by the softener.
  • the wastewater from the metalworking industry first pretreated by a flocculation or precipitation process for the removal of heavy metals from the wastewater.
  • flocculants metal salts or combination products are usually used.
  • the flocculants are added in a neutral to acidic medium.
  • the neutralization is then carried out by means of a lye, preferably sodium hydroxide, lime or the like. is used.
  • the resulting flakes are treated with a suitable separator z. B. deposited a diagonal clarifier.
  • a subsequent oil separator or Koaleszenzabscheider may be required, which then removes the free oil from the wastewater stream.
  • a suitable filter system for.
  • the wastewater then passes to a biological treatment stage.
  • This biological purification stage is usually designed as a trickling filter or fixed bed reactor.
  • the biological purification stage serves to reduce the chemical oxygen demand (COD).
  • the biological purification stage is assisted by blowing in oxygen.
  • the biological treatment stage may be followed by a fine filter which is intended to protect the membrane of the nanofiltration from coal erosion from the biological treatment stage.
  • a heat exchanger can be integrated, which increases or decreases the temperature as needed.
  • the wastewater is or multi-stage nanofiltration system supplied. Filter system, biological purification stage and nanofiltration system are backwashed as needed in a known manner.
  • the part of the wastewater stream remaining after the nanofiltration passes through the nanofiltration again.
  • the ratio of waste water flow, which passes through the nanofiltration again, to purified water is to be interpreted as required.
  • a ratio of 10 parts of wastewater to 1 part of purified water has been found.
  • the return to the nanofiltration has the advantage that the nanofiltration membrane can be chosen very fine, since the wastewater flow passes through the membrane several times.
  • the bleed pump ensures a constant pressure for the nanofiltration while the feed pump is set so that it replaces the amount of purified wastewater by supplying wastewater from the biofilter and thus ensures that the amount of liquid for the nanofiltration is constant.
  • the feed pump is set so that it replaces the amount of purified wastewater by supplying wastewater from the biofilter and thus ensures that the amount of liquid for the nanofiltration is constant.
  • the individual components are backwashed regularly.
  • the non-purified wastewater stream remaining after the nanofiltration is returned to the biological treatment stage for re-treatment.
  • This has the advantage that the COD is continuously reduced and fluctuations in the pollutant content are compensated.
  • the wastewater is also preferred in this arrangement in the feed and Bleedvon fed through a fine filter and a heat exchanger of nanofiltration. All filters require regular backwashing as above.
  • the wastewater stream is passed after passing through the nanofiltration through a filter system back into the biological purification stage and further passed as above preferred via a fine filter and a heat exchanger for nanofiltration.
  • the advantage over the aforementioned embodiment lies in the possibility of flocculating additional suspended matter before the wastewater stream is passed into the biofilter. Again, the filters are backwashed in a known manner.
  • FIG. 1 shows a schematic drawing of the wastewater treatment plant according to the invention.
  • the wastewater from production reaches the wastewater treatment plant according to the invention through one or more sewers 1, 1a.
  • the wastewater is first subjected to a flocculation or precipitation process 2, 2a for the removal of heavy metals from the wastewater.
  • the resulting flakes are in a suitable separator 3, 3a, z.
  • the pretreated wastewater stream then passes through a pumping station 4 to a filter system 5.
  • the filter system 5 serves to remove residual flocculation of the flocculation / precipitation 2, 2a.
  • the biofilter 6 of the COD is degraded with the biofilter 6 is preferably designed as a trickling filter or fixed bed reactor.
  • the feed pump 8 further promotes the treated wastewater stream over a Fine filter 9, to protect the membrane of the nanofiltration 12 before Kohleabrieb, a heat exchanger 10, for stabilizing the temperature, the nanofiltration 12.
  • the upstream Bleedpumpe 11 provides the necessary constant pressure in the nanofiltration 12.
  • the purified wastewater 13, advantageously approximately one One-tenth of the total wastewater stream leaves the nanofiltration plant 12 and can thus be returned to production.
  • the remaining wastewater is fed back via a line 14 according to the invention or the purification stages 5, 6, 12.
  • the return either via the valve 15 and the line 16 back to the nanofiltration 12 or via the valve 17 and the line 18 back into the filter. 5

Description

Die Erfindung bezieht sich auf ein Verfahren zur Aufbereitung von Abwässern aus der metallverarbeitenden Industrie, vorzugsweise dazu geeignet das Abwasser derart aufzubereiten, daß es der Produktion erneut zugeführt werden kann.The invention relates to a method for the treatment of waste water from the metalworking industry, preferably suitable for treating the wastewater so that it can be supplied to the production again.

In der metallverarbeitenden Industrie fallen häufig große Mengen an Abwassern an, z. B. aus der spanenden oder schleifenden Bearbeitung von Werkstücken in Form von Kühlschmiermitteln oder als Kühl- oder Spülwasser. Üblicherweise wird dieses Abwasser nach Durchlaufen einer entsprechenden Abwasserbehandlungsanlage (ABA) in die öffentliche Kanalisation abgegeben. Eine Mehrfachnutzung oder Wiederverwendung des Abwassers in der Produktion ist aus Kostengründen wünschenswert.In the metalworking industry are often large amounts of waste water, z. B. from the machining or grinding of workpieces in the form of cooling lubricants or as cooling or rinsing water. Usually, this wastewater is discharged into the public sewer after passing through a corresponding wastewater treatment plant (ABA). Multiple use or reuse of wastewater in production is desirable for cost reasons.

Die oben genannten Abwässer sind im Wesentlichen mit folgenden Schadstoffen belastet (als Grundlage dient hier die Rahmen-Abwasser VwV, Anhang 40): Tabelle 1: Schadstoffe im industriellen Abwasser und deren Behandlungsmöglichkeiten Parameter Behandlungsmethode in der ABA Schwermetalle Flockung / Fällung als Metallhydroxidschlamm, Bisulfidfällung, lonentauscher. CKW, LHKW Aktivkohle Komplexbildner Vermeidung Kohlenwasserstoffe Membranverfahren CSB Biologische Abbaustufe The abovementioned wastewater is essentially contaminated with the following pollutants (the framework wastewater VwV, Appendix 40) serves as the basis: Table 1: Pollutants in industrial wastewater and their treatment options parameter Treatment method in the ABA heavy metals Flocculation / Precipitation as Metallhydroxidschlamm, bisulfide precipitation, ion exchanger. CKW, LHKW activated carbon complexing avoidance hydrocarbons membrane processes CSB Biological degradation stage

Diese Schadstoffe werden heute mit entsprechenden chemischen oder physikalischen Verfahren behandelt - wie in o.g. Tabelle gezeigt - und abgeschieden. Dabei gilt es die gesetzlich festgelegten Konzentrationen einzuhalten. Insbesondere spielt die Ausflockung und/oder Ausfällung der Schadstoffe im Behandlungsprozeß eine zentrale Rolle, da nur mit diesen Verfahren große Wassermengen behandelt werden können. Als Nebenprodukt des Fällungsprozesses wird aber das Wasser mit Calcium-, Natrium-, Chlorid- und Sulfatverbindungen aufgesalzt.These pollutants are treated today with appropriate chemical or physical processes - as in o.g. Table shown - and deposited. It is important to comply with the legally stipulated concentrations. In particular, the flocculation and / or precipitation of the pollutants in the treatment process plays a central role, since only with these methods large amounts of water can be treated. As a by-product of the precipitation process, however, the water is salted up with calcium, sodium, chloride and sulfate compounds.

So ist aus der DE 37 09 174 ein Verfahren bekannt, welches eine Reinigung von organisch belastetem Abwasser beschreibt. Dabei werden die organischen Schadstoffe unter Überdruck mikrobiologisch umgesetzt und der entstehende biologische Schlamm durch eine Membran- oder Ultrafiltration vom Abwasser getrennt. Dieses Verfahren hat allerdings den Nachteil, daß biologisch schwer abbaubare organische Schadstoffe oder anorganische Schadstoffe, die von der Partikelgröße unterhalb der Membrantrenngrenze liegen nicht umgesetzt bzw. nicht abgetrennt werden, sondern im Abwasser verbleiben.Thus, from DE 37 09 174 a method is known which describes a purification of organically polluted wastewater. The organic pollutants are microbiologically reacted under pressure and the resulting biological sludge separated by a membrane or ultrafiltration from the wastewater. However, this method has the disadvantage that poorly biodegradable organic pollutants or inorganic pollutants that are of the particle size below the membrane separation limit not implemented or not separated, but remain in the wastewater.

In der EP 0 503 115 wird aufbauend auf die DE 37 09 174 ein Verfahren beschrieben, bei dem nicht nur die organischen biologisch abbaubaren Schadstoffe sondern auch die biologisch schwer oder nicht abbaubaren organischen sowie die anorganischen Schadstoffe aus dem Abwasser entfernt werden. Dabei werden die biologisch schwer oder nicht abbaubaren organischen Stoffe physikalisch und/oder chemisch so behandelt, daß sie einer biologischen Behandlung zugeführt werden können. Weiterhin werden insbesondere die Schadstoffe aufkonzentriert und durchlaufen so mehrfach die biologische Reinigung. Diese Aufkonzentrierung wird durch Membranfiltration, vorzugsweise Nanofiltration durchgeführt, wobei die Nanofiltration den Vorteil hat, daß in dem so behandelten Abwasser nur niedermolekular gelöste Inhaltsstoffe, vor allem Salze, verbleiben. Allerdings weist auch dieses Verfahren den Nachteil auf, daß das behandelte Abwasser nicht weiter verwendet wird, sondern in die Kanalisation abgegeben wird.In EP 0 503 115 a method is described based on DE 37 09 174, in which not only the organic biodegradable pollutants but also the biologically difficult or non-degradable organic and inorganic pollutants are removed from the wastewater. In this case, the biologically difficult or non-degradable organic substances are physically and / or chemically treated so that they can be fed to a biological treatment. Furthermore, the pollutants in particular are concentrated and thus undergo repeated biological purification. This concentration is carried out by membrane filtration, preferably nanofiltration, the nanofiltration has the advantage that in the thus treated wastewater only low molecular dissolved ingredients, especially salts, remain. However, this one also points Process has the disadvantage that the treated wastewater is no longer used, but is discharged into the sewer.

Aus der DE 38 15 271 ist ein Verfahren bekannt bei dem vor oder nach der biologischen Reinigungsstufe mindestens eines der folgenden Verfahren durchgeführt wird: Adsorption, Membranfiltration und/oder Oxidation. Allerdings weist auch dieses Verfahren den Nachteil auf, daß das behandelte Abwasser nicht weiter verwendet wird, sondern in die Kanalisation abgegeben wird.From DE 38 15 271 a method is known in which before or after the biological treatment stage at least one of the following methods is performed: adsorption, membrane filtration and / or oxidation. However, this method also has the disadvantage that the treated wastewater is no longer used, but is discharged into the sewer system.

Ein Verfahren zur Mehrfachnutzung von Abwässern ist schließlich bekannt aus der DE 199 23 796. Hierbei werden zusätzlich Qualitätskriterien für die Wiederverwendung des Abwassers in der Produktion angegeben: Tabelle 2: Qualitätsmerkmale mit Zielwerten im aufbereiteten Abwasser. Parameter Zielwerte CSB < 100 mg CaO < 50 mg Leitfähigkeit < 1000 mS/cm A method for multiple use of wastewater is finally known from DE 199 23 796. Here, additional quality criteria for the reuse of wastewater in production are given: Table 2: Quality characteristics with target values in treated wastewater. parameter targets CSB <100 mg CaO <50 mg conductivity <1000 mS / cm

Nach Durchlaufen einer geeigneten ABA wird das Abwasser zuerst durch einen Sandfilter geleitet. Danach durchläuft das Abwasser einen Festbettreaktor zum Abbau des CSB. Anschließend werden die Ca-Ionen in zwei abwechselnd arbeitenden Enthärtersäulen gegen Na-Ionen ausgetauscht. Die abschließende Nanofiltration dient dann zur Einstellung aller Qualitätsparameter des dann so gereinigten Abwassers. Nachteilig ist hier zu bewerten, daß bei diesem Verfahren eine relativ große Menge Abwasser anfällt sowie durch die Enthärteranlage noch ein zusätzlicher Abwasserstrom geschaffen wird.After passing through a suitable ABA, the wastewater is first passed through a sand filter. Thereafter, the waste water passes through a fixed bed reactor for the removal of the COD. Subsequently, the Ca ions are exchanged for Na ions in two alternating softening columns. The final nanofiltration then serves to set all the quality parameters of the wastewater that is then purified. The disadvantage here is to assess that in this method, a relatively large amount of wastewater is obtained as well as an additional wastewater stream is created by the softener.

Vor diesem Hintergrund war es die Aufgabe der vorliegenden Erfindung, ein Verfahren zu entwickeln, daß Industrieabwässer kontinuierlich so aufbereitet, daß es der Produktion wieder zur Verfügung steht und die Nachteile der vorher beschriebenen Verfahren vermeidet.Against this background, it was the object of the present invention to develop a process that continuously reprocesses industrial wastewater so that it is available again for production and avoids the disadvantages of the previously described processes.

Diese Aufgabe wird durch ein Verfahren zur Aufbereitung von Industrieabwässern mit den Merkmalen des Anspruches 1 gelöst. Weitere vorteilhafte Ausgestaltungen sind in den Unteransprüchen enthalten.This object is achieved by a process for the treatment of industrial wastewater having the features of claim 1. Further advantageous embodiments are contained in the subclaims.

Erfindungsgemäß wird das Abwasser aus der metallverarbeitenden Industrie, zunächst durch einen Flockungs- bzw. Fällungsprozeß zur Entfernung der Schwermetalle aus dem Abwasser vorbehandelt. Als Flockungshilfsmittel werden üblicherweise Metallsalze oder Kombinationsprodukte verwendet. Die Zugabe der Flockungshilfsmittel erfolgt im neutralen bis saueren Milieu. Die Neutralisation erfolgt dann mittels einer Lauge wobei bevorzugt Natronlauge, Kalkmilch o. Ä. verwendet wird. Die entstehenden Flocken werden mit einem geeigneten Abscheider z. B. einem Schrägklärer abgeschieden. Je nach Art des metallverarbeitenden Betriebes kann ein nachfolgender Ölabscheider oder Koaleszenzabscheider erforderlich sein, der dann das freie Öl aus dem Abwasserstrom entfernt. Über ein geeignetes Filtersystem, z. B. einen Sandfilter, zum Abscheiden von Restflocken und/oder Schwebstoffen gelangt das Abwasser dann zu einer biologischen Reinigungsstufe. Diese biologische Reinigungsstufe ist in der Regel als Tropfkörper oder Festbettreaktor ausgebildet. Dabei dient die biologische Reinigungsstufe zum Abbau des chemischen Sauerstoffbedarfs (CSB). Vorzugsweise wird die biologische Reinigungsstufe durch Einblasen von Sauerstoff unterstützt. Der biologischen Reinigungsstufe kann ein Feinfilter nachgeschaltet sein, der die Membran der Nanofiltration vor Kohleabrieb aus der biologischen Reinigungsstufe schützen soll. Zur Stabilisierung der Temperatur kann ein Wärmetauscher integriert sein, der je nach Bedarf die Temperatur erhöht oder erniedrigt. Letztendlich wird das Abwasser einer ein- oder mehrstufigen Nanofiltrationsanlage zugeführt. Filtersystem, biologische Reinigungsstufe und Nanofiltrationsanlage werden je nach Bedarf in bekannter Weise rückgespült.According to the invention, the wastewater from the metalworking industry, first pretreated by a flocculation or precipitation process for the removal of heavy metals from the wastewater. As flocculants, metal salts or combination products are usually used. The flocculants are added in a neutral to acidic medium. The neutralization is then carried out by means of a lye, preferably sodium hydroxide, lime or the like. is used. The resulting flakes are treated with a suitable separator z. B. deposited a diagonal clarifier. Depending on the type of metalworking operation, a subsequent oil separator or Koaleszenzabscheider may be required, which then removes the free oil from the wastewater stream. About a suitable filter system, for. As a sand filter, for the separation of residual flakes and / or suspended solids, the wastewater then passes to a biological treatment stage. This biological purification stage is usually designed as a trickling filter or fixed bed reactor. The biological purification stage serves to reduce the chemical oxygen demand (COD). Preferably, the biological purification stage is assisted by blowing in oxygen. The biological treatment stage may be followed by a fine filter which is intended to protect the membrane of the nanofiltration from coal erosion from the biological treatment stage. To stabilize the temperature, a heat exchanger can be integrated, which increases or decreases the temperature as needed. Ultimately, the wastewater is or multi-stage nanofiltration system supplied. Filter system, biological purification stage and nanofiltration system are backwashed as needed in a known manner.

In einer vorteilhaften Ausgestaltung der vorliegenden Erfindung durchläuft der nach der Nanofiltration verbleibende Teil des Abwasserstromes erneut die Nanofiltration. Das Verhältnis von Abwasserstrom, der die Nanofiltration erneut durchläuft, zu gereinigtem Wasser ist dabei je nach Bedarf auszulegen. Als vorteilhaft hat sich ein Verhältnis von 10 Teilen Abwasserstrom zu 1 Teil gereinigtem Wasser herausgestellt. Die Rückführung in die Nanofiltration weist dabei den Vorteil auf, daß die Nanofiltrationsmembran sehr fein gewählt werden kann, da der Abwasserstrom die Membran mehrfach passiert. Zusätzlich findet eine Aufkonzentration der Schadstoffe im Nanofiltrationskreislauf statt. Vorteilhaft ist es außerdem den Nanofiltrationskreislauf im Feed- and Bleedverfahren durchzuführen. Die Bleedpumpe sorgt dabei für einen gleichbleibenden Druck für die Nanofiltration während die Feedpumpe so eingestellt ist, daß sie die Menge des gereinigten Abwassers durch Zufuhr von Abwasser aus dem Biofilter ersetzt und so dafür sorgt, daß die Flüssigkeitsmenge für die Nanofiltration gleichbleibend ist. In die Zufuhr des Abwassers zur Nanofiltration können auch hier wieder wie zuvor ein Feinfilter und ein Wärmetauscher integriert sein. Auch bei dieser Anordnung werden die einzelnen Komponenten regelmäßig rückgespült.In an advantageous embodiment of the present invention, the part of the wastewater stream remaining after the nanofiltration passes through the nanofiltration again. The ratio of waste water flow, which passes through the nanofiltration again, to purified water is to be interpreted as required. As advantageous, a ratio of 10 parts of wastewater to 1 part of purified water has been found. The return to the nanofiltration has the advantage that the nanofiltration membrane can be chosen very fine, since the wastewater flow passes through the membrane several times. In addition, there is a concentration of pollutants in the nanofiltration circuit. It is also advantageous to carry out the nanofiltration cycle in the feed and bleed process. The bleed pump ensures a constant pressure for the nanofiltration while the feed pump is set so that it replaces the amount of purified wastewater by supplying wastewater from the biofilter and thus ensures that the amount of liquid for the nanofiltration is constant. In the supply of waste water for nanofiltration can again be integrated as before a fine filter and a heat exchanger. Also in this arrangement, the individual components are backwashed regularly.

In einer weiteren vorteilhaften Ausgestaltung der Erfindung wird der nach der Nanofiltration verbleibende nicht gereinigte Abwasserstrom wieder zurück zur erneuten Behandlung in die biologische Reinigungsstufe geführt. Dies hat den Vorteil, daß der CSB kontinuierlich abgebaut wird sowie Schwankungen im Schadstoffgehalt ausgeglichen werden. Weiterhin findet auch hier eine Aufkonzentration der Schadstoffe durch die Nanofiltration statt, die, wie oben bereits erwähnt, zum Teil in der biologischen Reinigungsstufe abgebaut werden. Das Abwasser wird auch in dieser Anordnung bevorzugt im Feed- und Bleedverfahren über einen Feinfilter und einen Wärmetauscher der Nanofiltration zugeführt. Alle Filter benötigen wie oben eine regelmäßige Rückspülung.In a further advantageous embodiment of the invention, the non-purified wastewater stream remaining after the nanofiltration is returned to the biological treatment stage for re-treatment. This has the advantage that the COD is continuously reduced and fluctuations in the pollutant content are compensated. Furthermore, there is also a concentration of pollutants by the nanofiltration here, which, as already mentioned above, are partially degraded in the biological treatment stage. The wastewater is also preferred in this arrangement in the feed and Bleedverfahren fed through a fine filter and a heat exchanger of nanofiltration. All filters require regular backwashing as above.

In einer weiteren bevorzugten Ausgestaltung der Erfindung wird der Abwasserstrom nach Passieren der Nanofiltration über ein Filtersystem zurück in die biologische Reinigungsstufe geführt und weiter wie oben bevorzugt über einen Feinfilter und einen Wärmetauscher zur Nanofiltration geleitet. Der Vorteil gegenüber der zuvor erwähnten Ausgestaltung liegt hierbei in der Möglichkeit zusätzlich Schwebstoffe auszuflocken, bevor der Abwasserstrom in den Biofilter geleitet wird. Auch hier werden die Filter in bekannter Weise zurückgespült.In a further preferred embodiment of the invention, the wastewater stream is passed after passing through the nanofiltration through a filter system back into the biological purification stage and further passed as above preferred via a fine filter and a heat exchanger for nanofiltration. The advantage over the aforementioned embodiment lies in the possibility of flocculating additional suspended matter before the wastewater stream is passed into the biofilter. Again, the filters are backwashed in a known manner.

Die Erfindung wird anhand des in der beiliegenden Zeichnung gezeigten Ausführungsbeispieles näher erläutert. Es zeigt

Fig. 1
eine schematischen Skizze einer bevorzugten Ausführung der erfindungsgemäßen Abwasserreinigungsanlage
The invention will be explained in more detail with reference to the embodiment shown in the accompanying drawings. It shows
Fig. 1
a schematic sketch of a preferred embodiment of the wastewater treatment plant according to the invention

In Figur 1 zeigt eine schematische Zeichnung der erfindungsgemäßen Abwasserreinigungsanlage. Das Abwasser aus der Produktion erreicht die erfindungsgemäße Abwasserreinigungsanlage durch eine oder mehrere Abwasserleitungen 1, 1a. Das Abwasser wird zunächst einem Flockungs- bzw. Fällungsprozeß 2, 2a zur Entfernung der Schwermetalle aus dem Abwasser unterzogen. Die entstehenden Flocken werden in einem geeigneten Abscheider 3, 3a, z. B. einem Schrägklärer (hier gezeigt) abgeschieden. Der so vorbehandelte Abwasserstrom gelangt dann über eine Pumpstation 4 zu einem Filtersystem 5. Das Filtersystem 5 dient dazu Restflocken der Flockung/Fällung 2, 2a zu entfernen. Im anschließenden Biofilter 6 wird der CSB abgebaut wobei der Biofilter 6 bevorzugt als Tropfkörper oder Festbettreaktor ausgeführt ist. Zur Unterstützung wird zusätzlich Sauerstoff 7 in den Biofilter 6 eingeblasen. Die Feedpumpe 8 fördert den so behandelten Abwasserstrom weiter über einen Feinfilter 9, zum Schutz der Membrane der Nanofiltration 12 vor Kohleabrieb, einen Wärmetauscher 10, zur Stabilisierung der Temperatur, zur Nanofiltrationsanlage 12. Hierbei sorgt die vorgeschaltete Bleedpumpe 11 für den nötigen gleichbleibenden Druck in der Nanofiltrationsanlage 12. Das gereinigte Abwasser 13, vorteilhafterweise ungefähr ein Zehntel des Gesamtabwasserstroms, verläßt die Nanofiltrationsanlage 12 und kann somit der Produktion wieder zugeführt werden. Das verbleibende Abwasser wird über eine Leitung 14 erfindungsgemäß wieder der oder den Reinigungsstufen 5, 6, 12 zugeführt. Dabei erfolgt bei dieser Ausführung die Rückführung entweder über das Ventil 15 und die Leitung 16 zurück zur Nanofiltration 12 oder über das Ventil 17 und die Leitung 18 zurück in den Filter 5.FIG. 1 shows a schematic drawing of the wastewater treatment plant according to the invention. The wastewater from production reaches the wastewater treatment plant according to the invention through one or more sewers 1, 1a. The wastewater is first subjected to a flocculation or precipitation process 2, 2a for the removal of heavy metals from the wastewater. The resulting flakes are in a suitable separator 3, 3a, z. As a diagonal clarifier (shown here) deposited. The pretreated wastewater stream then passes through a pumping station 4 to a filter system 5. The filter system 5 serves to remove residual flocculation of the flocculation / precipitation 2, 2a. In the subsequent biofilter 6 of the COD is degraded with the biofilter 6 is preferably designed as a trickling filter or fixed bed reactor. To support additional oxygen 7 is injected into the biofilter 6. The feed pump 8 further promotes the treated wastewater stream over a Fine filter 9, to protect the membrane of the nanofiltration 12 before Kohleabrieb, a heat exchanger 10, for stabilizing the temperature, the nanofiltration 12. Here, the upstream Bleedpumpe 11 provides the necessary constant pressure in the nanofiltration 12. The purified wastewater 13, advantageously approximately one One-tenth of the total wastewater stream leaves the nanofiltration plant 12 and can thus be returned to production. The remaining wastewater is fed back via a line 14 according to the invention or the purification stages 5, 6, 12. In this embodiment, in this embodiment, the return either via the valve 15 and the line 16 back to the nanofiltration 12 or via the valve 17 and the line 18 back into the filter. 5

Claims (4)

  1. Process for treating and thus for treating wastewaters polluted with heavy metals, the wastewater (1, 1 a) passing through
    - at least one chemical/physical flocculation/precipitation (2, 2a),
    - a filter system (5),
    - a biological wastewater purification stage (6),
    - and also a nanofiltration unit (12),
    wastewaters from the metal-processing industry characterized in that,
    the wastewater (1, 1a), as part of a pretreatment, passes first through the chemical/physical flocculation/precipitation (2, 2a), i.e. before the filter system(s), before the biological wastewater purification stage (6) and before the nanofiltration unit (12).
  2. Process according to Claim 1,
    characterized in that
    the wastewater stream (14), after passing through the nanofiltration (12) is fed back for renewed nanofiltration (12).
  3. Process according to Claim 1,
    characterized in that
    the wastewater stream (14), after passing through the nanofiltration (12), is fed back to the biological purification stage (6) for renewed treatment.
  4. Process according to Claim 1,
    characterized in that
    the wastewater stream (14), after passing through the nanofiltration (12), is fed back into the biological purification stage (5) via a filter system (6).
EP20020100091 2002-01-31 2002-01-31 Method for treating industrial waste water Expired - Lifetime EP1293485B1 (en)

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DE50206295T DE50206295D1 (en) 2002-01-31 2002-01-31 Process for the treatment of industrial wastewater
ES02100091T ES2261595T3 (en) 2002-01-31 2002-01-31 PROCEDURE FOR THE TREATMENT OF INDUSTRIAL WASTEWATER.
EP20020100091 EP1293485B1 (en) 2002-01-31 2002-01-31 Method for treating industrial waste water
US10/248,589 US6787037B2 (en) 2002-01-31 2003-01-30 Process for treating industrial wastewaters

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US6787037B2 (en) 2004-09-07

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